CN115321507A - Method for preparing ferromanganese phosphate by coprecipitation and application thereof - Google Patents
Method for preparing ferromanganese phosphate by coprecipitation and application thereof Download PDFInfo
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- CN115321507A CN115321507A CN202211026776.1A CN202211026776A CN115321507A CN 115321507 A CN115321507 A CN 115321507A CN 202211026776 A CN202211026776 A CN 202211026776A CN 115321507 A CN115321507 A CN 115321507A
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- manganese
- phosphate
- ferricyanide
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- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 25
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 21
- 239000010452 phosphate Substances 0.000 title claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 20
- 238000000975 co-precipitation Methods 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000002585 base Substances 0.000 claims abstract description 16
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002696 manganese Chemical class 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- 239000011572 manganese Substances 0.000 claims description 26
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- -1 potassium ferricyanide Chemical compound 0.000 claims description 4
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 3
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 abstract description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 6
- 239000005955 Ferric phosphate Substances 0.000 abstract description 4
- 229940032958 ferric phosphate Drugs 0.000 abstract description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052748 manganese Inorganic materials 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 16
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910016953 Fe0.5Mn0.5PO4 Inorganic materials 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing ferromanganese phosphate by coprecipitation and application thereof, which comprises the steps of respectively preparing ferricyanide solution, manganese salt solution and mixed solution of phosphoric acid and perchloric acid, adding ferricyanide solution, manganese salt solution, mixed solution and alkali liquor into base liquor in a parallel flow manner for reaction, carrying out solid-liquid separation when reaction materials reach target particle size, obtaining precipitate, washing and drying to obtain ferromanganese phosphate. The invention utilizes ferricyanide to inhibit the direct precipitation of ferric ions, and perchloric acid and phosphoric acid are used for carrying out cyanogen breaking reaction, so that the precipitation rate of ferric phosphate is slowed down, the ferro-manganese is coprecipitated, and the uniformity of ferro-manganese mixing is improved.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode material precursors, and particularly relates to a method for preparing ferromanganese phosphate by coprecipitation and application thereof.
Background
The lithium iron phosphate has the defects of low electronic conductivity, small lithium ion diffusion coefficient and low material tap density in battery application, and because the manganese compound has high electrochemical reaction voltage and good electrolyte compatibility, the application of the lithium iron phosphate is widened by introducing the manganese compound into the lithium iron phosphate at present to form a lithium iron manganese phosphate solid solution so as to obtain good capacitance and cycle effect.
The synthesis method of lithium iron manganese phosphate is various and basically similar to the synthesis of lithium iron phosphate. The pure solid phase method comprises the steps of directly sintering raw materials such as a phosphorus source, an iron source, a manganese source, a lithium source and the like to obtain the lithium manganese iron phosphate, or synthesizing manganese phosphate as the manganese source and part of the phosphorus source, mixing the manganese phosphate, the iron source and the lithium source, and sintering to obtain the lithium manganous iron phosphate. The method has the defects that the uniform mixing of manganese and iron on the atomic layer can not be realized, and the prepared manganese lithium iron phosphate has poor charging constant voltage section and rate discharge performance. Because the Ksp of manganese phosphate is different from that of iron phosphate, and the precipitation rate is different from pH, the direct adoption of a coprecipitation method to prepare ferromanganese phosphate also has the problem that the ferromanganese is difficult to form a coprecipitate. In addition, the manganese in the synthesized ferromanganese phosphate exists mostly as bivalent manganese, and a phosphorus source needs to be additionally supplemented during subsequent sintering with a lithium source. And the direct use of trivalent manganese in the solution is easy to cause disproportionation reaction to generate bivalent manganese and tetravalent manganese, which affects the purity of the product.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a method for preparing ferromanganese phosphate by coprecipitation and application thereof, the process can slow down the precipitation rate of ferric phosphate, so that iron and manganese are coprecipitated, and the ferromanganese in the prepared ferromanganese phosphate is distributed more uniformly.
According to one aspect of the invention, the method for preparing the manganese iron phosphate by coprecipitation comprises the following steps:
s1: respectively preparing a ferricyanide solution, a manganese salt solution and a mixed solution of phosphoric acid and perchloric acid;
s2: mixing the mixed solution with alkali liquor to serve as base liquor, adding the ferricyanide solution, the manganese salt solution, the mixed solution and the alkali liquor into the base liquor in a parallel flow manner for reaction, and performing solid-liquid separation when the reaction material reaches a target particle size to obtain a precipitate;
s3: and washing and drying the precipitate to obtain the ferromanganese phosphate.
In some embodiments of the invention, in step S1, the ferricyanide solution is a solution comprising at least one of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide or potassium ferricyanide.
In some embodiments of the invention, in step S1, the concentration of the ferricyanide solution is 0.1-1.0mol/L.
In some embodiments of the present invention, in step S1, the manganese salt in the manganese salt solution is selected from at least one of manganese nitrate and manganese sulfate.
In some embodiments of the invention, the concentration of the manganese salt solution in step S1 is 0.1 to 1.0mol/L.
In some embodiments of the present invention, in step S1, the molar ratio of phosphoric acid to perchloric acid in the mixed solution is 1: (0.9-3.5).
In some embodiments of the present invention, in step S1, the total concentration of phosphoric acid and perchloric acid in the mixed solution is 0.5 to 1.0mol/L.
In some embodiments of the invention, in step S2, the pH of the base solution is 1.8 to 2.0.
In some embodiments of the invention, in step S2, the temperature of the reaction is controlled to be 50 to 70 ℃ and the pH is controlled to be 1.8 to 2.0.
In some embodiments of the present invention, in step S2, the molar ratio of the ferricyanide solution, the manganese salt solution and the mixed solution is controlled to satisfy: iron to manganese ratio＝(0.25-4)：1，(Fe+Mn)：H 3 PO 4 ＝1：(1.02-1.05)。
In some embodiments of the invention, in step S2, the alkali solution is at least one of a sodium hydroxide solution or a potassium hydroxide solution.
In some embodiments of the present invention, in step S2, the concentration of the lye is 0.5 to 1.0mol/L.
In some embodiments of the invention, in step S2, the reaction is carried out with stirring at a speed of 150 to 300 r/min.
In some embodiments of the invention, in step S2, the target particle diameter D50 is 2 to 15 μm.
In some embodiments of the present invention, in step S3, the drying is vacuum drying, the drying temperature is 120 to 150 ℃, and the drying time is 2 to 4 hours.
The invention also provides application of the method in preparation of lithium iron manganese phosphate or lithium ion batteries.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the method generates the ferromanganese phosphate coprecipitate by utilizing the coprecipitation reaction of ferricyanide and manganese salt in a medium of phosphoric acid and perchloric acid. The reaction equation is as follows (taking sodium ferricyanide as an example):
4Na 3 [Fe(CN) 6 ]+15HClO 4 +4H 3 PO 4 →24CO 2 ↑+12N 2 ↑+12NaCl+12H 2 O+4FePO 4 ↓+3HCl；
14Mn 2+ +14H 3 PO 4 +2HClO 4 →14MnPO 4 ↓+Cl 2 ↑+8H 2 O+28H + 。
2. when the ferromanganese phosphate is prepared, on one hand, iron and manganese are co-precipitated with phosphate radicals in a positive trivalent state to form ferromanganese phosphate, so that the problem that the phosphorus source is insufficient due to divalent cation precipitation and needs to be additionally supplemented in the subsequent process is solved, and the problem that the distribution of the ferromanganese phosphate is uneven is solved; on the other hand, because the Ksp of the ferric phosphate and the manganese phosphate is large in difference, iron is difficult to directly perform coprecipitation reaction with manganese, the direct precipitation of ferric ions is inhibited by using ferricyanide, and the cyanogen breaking reaction is performed by using perchloric acid and phosphoric acid, so that the precipitation rate of the ferric phosphate is slowed down, the iron and manganese are coprecipitated, the uniformity of iron and manganese mixing is improved, and a foundation is laid for improving the specific capacity and the cycle performance of a material for subsequent sintering of the lithium iron manganese phosphate positive electrode material.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is an SEM photograph of ferromanganese phosphate prepared in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The preparation method of the manganese iron phosphate comprises the following specific steps:
step 1, preparing a sodium ferricyanide solution with the concentration of 1.0mol/L;
step 2, preparing a manganese nitrate solution with the concentration of 1.0mol/L;
step 3, preparing a mixed solution of phosphoric acid and perchloric acid with the total concentration of 1.0mol/L according to a molar ratio of phosphoric acid to perchloric acid = 1;
step 4, preparing a sodium hydroxide solution with the concentration of 1.0mol/L;
step 5, adding the solution prepared in the step 3 and the step 4 into a reaction kettle to be used as a base solution, wherein the base solution overflows a bottom stirring paddle, and the pH value of the base solution is 1.8-2.0;
and 6, adding the solutions prepared in the steps 1, 2, 3 and 4 into a reaction kettle in a concurrent flow manner, controlling the molar ratio of the materials fed into the reaction kettle, wherein the iron-manganese ratio is 1 3 PO 4 1, controlling the pH value in the reaction kettle to be 1.8-2.0, and controlling the stirring speed to be 250r/min, wherein the reaction temperature is 70 ℃;
step 7, stopping feeding when detecting that the D50 of the material in the kettle reaches 10.5 mu m, and carrying out solid-liquid separation to obtain a precipitate;
step 8, washing the precipitate with deionized water, and then washing with absolute ethyl alcohol;
and 9, placing the washed product at 135 ℃ for vacuum drying for 3 hours to obtain the manganese iron phosphate product.
Example 2
The manganese iron phosphate is prepared by the embodiment through the specific process:
step 1, preparing a potassium ferricyanide solution with the concentration of 0.5 mol/L;
step 2, preparing a manganese sulfate solution with the concentration of 0.5 mol/L;
step 3, preparing a mixed solution of phosphoric acid and perchloric acid with the total concentration of 1.0mol/L according to the molar ratio of phosphoric acid to perchloric acid =1: 0.9;
step 4, preparing a sodium hydroxide solution with the concentration of 0.5 mol/L;
step 5, adding the solution prepared in the step 3 and the step 4 into a reaction kettle to be used as a bottom solution, wherein the bottom solution overflows a bottom stirring paddle, and the pH value of the bottom solution is 1.8-2.0;
and 6, adding the solutions prepared in the steps 1, 2, 3 and 4 into a reaction kettle in a concurrent flow manner, controlling the molar ratio of the fed materials of the reaction kettle, wherein the ratio of iron to manganese is 0.25 3 PO 4 1, controlling the pH value in the reaction kettle to be 1.8-2.0, stirring at a rotating speed of 300r/min, and controlling the reaction temperature to be 60 ℃;
step 7, stopping feeding when detecting that the D50 of the material in the kettle reaches 2 mu m, and carrying out solid-liquid separation to obtain a precipitate;
step 8, washing the precipitate with deionized water, and then washing with absolute ethyl alcohol;
and 9, placing the washed product at 120 ℃ for vacuum drying for 4 hours to obtain the manganese iron phosphate product.
Example 3
The manganese iron phosphate is prepared by the embodiment through the specific process:
step 1, preparing a sodium ferrocyanide solution with the concentration of 0.1 mol/L;
step 2, preparing a manganese nitrate solution with the concentration of 0.1 mol/L;
step 3, preparing a mixed solution of phosphoric acid and perchloric acid with the total concentration of 0.5mol/L according to the molar ratio of phosphoric acid to perchloric acid =1: 3.5;
step 4, preparing a sodium hydroxide solution with the concentration of 0.5 mol/L;
step 5, adding the solution prepared in the step 3 and the step 4 into a reaction kettle to be used as a bottom solution, wherein the bottom solution overflows a bottom stirring paddle, and the pH value of the bottom solution is 1.8-2.0;
and 6, adding the solutions prepared in the steps 1, 2, 3 and 4 into a reaction kettle in a concurrent flow manner, controlling the molar ratio of the fed materials of the reaction kettle, wherein the ratio of iron to manganese is 1 3 PO 4 1, controlling the pH value in the reaction kettle to be 1.8-2.0, the stirring speed to be 150r/min, and the reaction temperature to be 50 ℃;
step 7, stopping feeding when detecting that the D50 of the material in the kettle reaches 15 mu m, and carrying out solid-liquid separation to obtain a precipitate;
step 8, washing the precipitate with deionized water, and then washing with absolute ethyl alcohol;
and 9, placing the washed product at 150 ℃ for vacuum drying for 2h to obtain the manganese iron phosphate product.
Comparative example 1
The manganese iron phosphate prepared by the comparative example is different from that prepared by the example 1 in that iron nitrate is adopted as an iron source, and the specific process is as follows:
step 1, preparing a ferric nitrate solution with the concentration of 1.0mol/L;
step 2, preparing a manganese nitrate solution with the concentration of 1.0mol/L;
step 3, preparing a mixed solution of phosphoric acid and perchloric acid with the total concentration of 1.0mol/L according to the molar ratio of phosphoric acid to perchloric acid = 1;
step 4, preparing a sodium hydroxide solution with the concentration of 1.0mol/L;
step 5, adding the solution prepared in the step 3 and the step 4 into a reaction kettle to be used as a base solution, wherein the base solution overflows a bottom stirring paddle, and the pH value of the base solution is 1.8-2.0;
and 6, adding the solutions prepared in the steps 1, 2, 3 and 4 into a reaction kettle in a concurrent flow manner, controlling the molar ratio of the materials fed into the reaction kettle, wherein the iron-manganese ratio is 1 3 PO 4 1, controlling the pH value in the reaction kettle to be 1.8-2.0, and controlling the stirring speed to be 250r/min, wherein the reaction temperature is 70 ℃;
step 7, stopping feeding when detecting that the D50 of the material in the kettle reaches 10.5 microns, and carrying out solid-liquid separation to obtain a precipitate;
step 8, washing the precipitate with deionized water, and then washing with absolute ethyl alcohol;
and 9, placing the washed product at 135 ℃ for vacuum drying for 3 hours to obtain the manganese iron phosphate product.
Comparative example 2
The manganese iron phosphate prepared by the comparative example is different from that prepared by the example 2 in that the iron source adopts ferric sulfate and the specific process is as follows:
step 1, preparing a ferric sulfate solution with the concentration of 0.5 mol/L;
step 2, preparing a manganese sulfate solution with the concentration of 0.5 mol/L;
step 3, preparing a mixed solution of phosphoric acid and perchloric acid with the total concentration of 1.0mol/L according to the molar ratio of phosphoric acid to perchloric acid =1: 0.9;
step 4, preparing a sodium hydroxide solution with the concentration of 0.5 mol/L;
step 5, adding the solution prepared in the step 3 and the step 4 into a reaction kettle to be used as a base solution, wherein the base solution overflows a bottom stirring paddle, and the pH value of the base solution is 1.8-2.0;
and 6, adding the solutions prepared in the steps 1, 2, 3 and 4 into a reaction kettle in a concurrent flow manner, controlling the molar ratio of the fed materials of the reaction kettle, wherein the ratio of iron to manganese is 0.25 3 PO 4 1, controlling the pH value in the reaction kettle to be 1.8-2.0, stirring at a rotating speed of 300r/min, and controlling the reaction temperature to be 60 ℃;
step 7, stopping feeding when detecting that the D50 of the material in the kettle reaches 2 microns, and carrying out solid-liquid separation to obtain a precipitate;
step 8, washing the precipitate with deionized water, and then washing with absolute ethyl alcohol;
and 9, placing the washed product at 120 ℃ for vacuum drying for 4 hours to obtain a manganese iron phosphate product.
Comparative example 3
The manganese iron phosphate prepared by the comparative example is different from the manganese iron phosphate prepared by the example 3 in that the iron source adopts ferrous nitrate, and the specific process is as follows:
step 1, preparing a ferrous nitrate solution with the concentration of 0.1 mol/L;
step 2, preparing a manganese nitrate solution with the concentration of 0.1 mol/L;
step 3, preparing a mixed solution of phosphoric acid and perchloric acid with the total concentration of 0.5mol/L according to a molar ratio of phosphoric acid to perchloric acid =1: 3.5;
step 4, preparing a sodium hydroxide solution with the concentration of 0.5 mol/L;
step 5, adding the solution prepared in the step 3 and the step 4 into a reaction kettle to be used as a bottom solution, wherein the bottom solution overflows a bottom stirring paddle, and the pH value of the bottom solution is 1.8-2.0;
and 6, adding the solutions prepared in the steps 1, 2, 3 and 4 into a reaction kettle in a concurrent flow manner, controlling the molar ratio of the materials fed into the reaction kettle, wherein the iron-manganese ratio is 4 3 PO 4 1, controlling the pH value in the reaction kettle to be 1.8-2.0, the stirring speed to be 150r/min, and the reaction temperature to be 50 ℃;
step 7, stopping feeding when detecting that the D50 of the material in the kettle reaches 15 microns, and carrying out solid-liquid separation to obtain a precipitate;
step 8, washing the precipitate with deionized water, and then washing with absolute ethyl alcohol;
and 9, placing the washed product at 150 ℃ for vacuum drying for 2h to obtain the manganese iron phosphate product.
Comparative example 4
The comparative example prepares manganese iron phosphate, and is different from the example 1 in that the iron source adopts ferric nitrate and perchloric acid is not added, and the specific process is as follows:
step 1, preparing a ferric nitrate solution with the concentration of 1.0mol/L;
step 2, preparing a manganese nitrate solution with the concentration of 1.0mol/L;
step 3, preparing a phosphoric acid solution with the concentration of 1.0mol/L;
step 4, preparing a sodium hydroxide solution with the concentration of 1.0mol/L;
step 5, adding the solution prepared in the step 3 and the step 4 into a reaction kettle to be used as a bottom solution, wherein the bottom solution overflows a bottom stirring paddle, and the pH value of the bottom solution is 1.8-2.0;
and 6, adding the solutions prepared in the steps 1, 2, 3 and 4 into a reaction kettle in a concurrent flow manner, controlling the molar ratio of the materials fed into the reaction kettle, wherein the iron-manganese ratio is 1 3 PO 4 1, controlling the pH value in the reaction kettle to be 1.8-2.0, and controlling the stirring speed to be 250r/min, wherein the reaction temperature is 70 ℃;
step 7, stopping feeding when detecting that the D50 of the material in the kettle reaches 10.5 mu m, and carrying out solid-liquid separation to obtain a precipitate;
step 8, washing the precipitate with deionized water, and then washing with absolute ethyl alcohol;
and 9, placing the washed product at 135 ℃ for vacuum drying for 3 hours to obtain the manganese iron phosphate product.
ICP measurements were performed on the ferromanganese phosphate products obtained in examples 1 to 3 and comparative examples 1 to 4, and the results are shown in Table 1.
TABLE 1
| Fe/％ | Mn/％ | P/％ | Fe:Mn:P | Formula of computer | |
| Example 1 | 18.566 | 18.270 | 20.601 | 0.5:0.5:1 | Fe 0.5 Mn 0.5 PO 4 |
| Example 2 | 7.442 | 29.281 | 20.637 | 0.2:0.8:1 | Fe 0.2 Mn 0.8 PO 4 |
| Example 3 | 18.568 | 18.267 | 20.603 | 0.5:0.5:1 | Fe 0.5 Mn 0.5 PO 4 |
| Comparative example 1 | 32.602 | 4.377 | 20.552 | 0.88:0.12:1 | Fe 0.88 Mn 0.12 PO 4 |
| Comparative example 2 | 32.606 | 4.377 | 20.553 | 0.88:0.12:1 | Fe 0.88 Mn 0.12 PO 4 |
| Comparative example 3 | 32.605 | 4.378 | 20.553 | 0.88:0.12:1 | Fe 0.88 Mn 0.12 PO 4 |
| Comparative example 4 | 36.234 | 1.068 | 20.459 | 1:0.03:1.02 | FePO 4 ·0.01Mn 3 (PO 4 ) 2 |
As can be seen from the test results in table 1, the precipitation amount of manganese in each comparative example is very small, and even if manganese is increased to the maximum amount, the precipitation amount of manganese is still very small, and the desired ferromanganese phosphate target product cannot be obtained.
Test examples
Mixing the ferromanganese phosphate products obtained in examples 1 to 3 and comparative examples 1 to 4 with lithium hydroxide and glucose respectively according to a molar ratio (Fe + Mn) of Li to a carbon source = 1.1; calcining for 16h at 750 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain the finished product of the lithium iron manganese phosphate cathode material.
The lithium iron manganese phosphate positive electrode materials obtained in the examples and the comparative examples are prepared by taking acetylene black as a conductive agent and PVDF as a viscous materialThe binder is mixed according to the mass ratio of 8; the diaphragm is Celgard2400 polypropylene porous membrane; the solvent in the electrolyte is a solution composed of EC, DMC and EMC according to a mass ratio of 1 6 ，LiPF 6 The concentration of (A) is 1.0mol/L; a 2023 button cell battery was assembled in the glove box. Carrying out charge-discharge cycle performance test on the battery, and testing the discharge specific capacity of 0.2C and 1C within the range of cut-off voltage of 2.2-4.3V; the results of testing electrochemical performance are shown in table 2.
TABLE 2
It can be seen from table 2 that the electrochemical performance of the embodiment is significantly better than that of the comparative example, which indicates that the lithium manganese iron phosphate obtained by sintering the prepared ferric manganese phosphate has higher specific capacity and cycle performance.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The method for preparing the ferromanganese phosphate by coprecipitation is characterized by comprising the following steps:
s1: respectively preparing a ferricyanide solution, a manganese salt solution and a mixed solution of phosphoric acid and perchloric acid;
s2: mixing the mixed solution with alkali liquor to serve as base liquor, adding the ferricyanide solution, the manganese salt solution, the mixed solution and the alkali liquor into the base liquor in a parallel flow manner for reaction, and performing solid-liquid separation when the reaction material reaches a target particle size to obtain a precipitate;
s3: and washing and drying the precipitate to obtain the ferromanganese phosphate.
2. The method according to claim 1, wherein in step S1, the ferricyanide solution is a solution containing at least one of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide, or potassium ferricyanide.
3. The method as claimed in claim 1, wherein the concentration of the ferricyanide solution in step S1 is 0.1-1.0mol/L.
4. The method according to claim 1, wherein in step S1, the manganese salt in the manganese salt solution is selected from at least one of manganese nitrate and manganese sulfate.
5. The method according to claim 1, wherein in step S1, the molar ratio of phosphoric acid to perchloric acid in the mixed solution is 1: (0.9-3.5).
6. The method according to claim 1, wherein the pH of the base solution in step S2 is 1.8 to 2.0.
7. The method according to claim 1, wherein in step S2, the reaction temperature is controlled to 50 to 70 ℃ and the pH is controlled to 1.8 to 2.0.
8. The method of claim 1, wherein in step S2, the molar ratio of the ferricyanide solution, the manganese salt solution and the mixed solution is controlled to satisfy: ferro manganese ratio = (0.25-4): 1, (Fe + Mn): h 3 PO 4 ＝1：(1.02-1.05)。
9. The method of claim 1, wherein in step S2, the alkali solution is at least one of a sodium hydroxide solution or a potassium hydroxide solution.
10. Use of a method according to any one of claims 1 to 9 for the preparation of lithium iron manganese phosphate or lithium ion batteries.
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| CN202211026776.1A CN115321507B (en) | 2022-08-25 | 2022-08-25 | Method for preparing ferric manganese phosphate by coprecipitation and application thereof |
| PCT/CN2023/079081 WO2024040903A1 (en) | 2022-08-25 | 2023-03-01 | Method for preparing ferromanganese phosphate by coprecipitation and use thereof |
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| CN116062726A (en) * | 2023-03-09 | 2023-05-05 | 金驰能源材料有限公司 | Lithium iron phosphate and continuous production method thereof |
| WO2024040903A1 (en) * | 2022-08-25 | 2024-02-29 | 广东邦普循环科技有限公司 | Method for preparing ferromanganese phosphate by coprecipitation and use thereof |
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| CN104518217A (en) * | 2015-01-20 | 2015-04-15 | 杨志宽 | Battery grade iron and manganese phosphate and preparation method thereof |
| US20160072129A1 (en) * | 2013-05-08 | 2016-03-10 | Advanced Lithium Electrochemistry Co., Ltd. | Preparation method of battery composite material and precursor thereof |
| CN107697899A (en) * | 2017-10-31 | 2018-02-16 | 中钢集团安徽天源科技股份有限公司 | Preparation method, lithium ferric manganese phosphate, cell positive material and the secondary cell of battery-grade iron phosphate manganese |
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| JP5429980B2 (en) * | 2009-11-05 | 2014-02-26 | テイカ株式会社 | Method for producing carbon-olivine-type manganese iron phosphate lithium composite and positive electrode material for lithium ion battery |
| CN115321507B (en) * | 2022-08-25 | 2023-07-07 | 广东邦普循环科技有限公司 | Method for preparing ferric manganese phosphate by coprecipitation and application thereof |
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| US20160072129A1 (en) * | 2013-05-08 | 2016-03-10 | Advanced Lithium Electrochemistry Co., Ltd. | Preparation method of battery composite material and precursor thereof |
| CN104518217A (en) * | 2015-01-20 | 2015-04-15 | 杨志宽 | Battery grade iron and manganese phosphate and preparation method thereof |
| CN107697899A (en) * | 2017-10-31 | 2018-02-16 | 中钢集团安徽天源科技股份有限公司 | Preparation method, lithium ferric manganese phosphate, cell positive material and the secondary cell of battery-grade iron phosphate manganese |
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| WO2024040903A1 (en) * | 2022-08-25 | 2024-02-29 | 广东邦普循环科技有限公司 | Method for preparing ferromanganese phosphate by coprecipitation and use thereof |
| CN116062726A (en) * | 2023-03-09 | 2023-05-05 | 金驰能源材料有限公司 | Lithium iron phosphate and continuous production method thereof |
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